Azobisisobutyronitrile Research Articles

Controllable and lightweight ZIF-67@PAN derived Co@C nanocomposites with tunable and broadband microwave absorption

Metal-organic framework-based carbon–carbon composite represent a novel class of microwave-absorbing materials (MAMs). However, obtaining lightweight and highly efficient absorbers with a lower filling ratio and larger effective absorption bandwidth (EAB) poses a challenge. In this study, we developed a controllable preparation method for ZIF-67 template polyacrylonitrile-wrapped nanocomposite (ZIF-67@PAN) precursor. This was achieved through radical polymerization of acrylonitrile (AN) initiated by azobisisobutyronitrile (AIBN). Subsequent annealing at high temperatures produced a lightweight nitrogen and oxygen-doped graphite layer-wrapped Co@C smart material (Co@C1, Co@C2, and Co@C3) with tunable microwave absorption properties (MAP). The results demonstrate that Co@C2 achieved a minimum reflection loss (RLmin) value of −50.20 dB at a thickness of 2.0 mm with an EAB of 6.1 only at a filler content of only 13 %. Therefore, this work offers a controllable preparation method and introduces a simple and facile approach for creating efficient, lightweight micro and nano-sized microwave-absorbing materials.

A facile and selective resonance Rayleigh scattering method for trace nitrite using gold nanocluster surface molecularly imprinted polyisopropylacrylamide probe.

A novel gold nanocluster surface molecularly imprinted polyisopropylacrylamide probe (AuNC@MIP) was synthesized for the specific detection of NO2-, using N-isopropylacrylamide (NIPAM) as the functional monomer, gold nanoclusters (AuNC) as the substrate, ethylene glycol dimethacrylate (EGDMA) as the cross-linking agent, and nitrosophenol (NPN) produced from sodium nitrite (NaNO2) and phenol (PN) as the template molecule, N,N-dimethylformamide (DMF) as the solvent, and azobisisobutyronitrile (AIBN) as the initiator. The nanoprobe was characterized using molecular spectroscopy, XPS, TEM, TGA, and zeta potential analysis. The probes revealed a prominent resonance Rayleigh scattering (RRS) peak at 370 nm. Upon addition of NO2-, the RRS intensity at 370 nm decreased due to the RRS energy transfer enhancing. The linear determination range is 0.125-1.50 nmol/L NO2-, with a limit of detection (LOD) of 0.085 nmol/L. The new RRS method was applied to determine NO2- in meat, dairy products, and water samples, with recovery of 96-107% also relative standard deviations (RSDs) of 1.1-8.0%.

Molecularly imprinted electrochemical sensor based on APTES-functionalized indium tin oxide electrode for the determination of sulfadiazine.

Anelectrochemical sensor was developedfor the sensitive and selective detection of sulfadiazine(SDZ), based on a molecularly imprinted polymer (MIP) film formed on an indium tin oxide (ITO) electrode through a self-assembly process. The SDZ-imprinted ITO electrode (SDZ-MIP/APTES-ITO) was prepared through in situ polymerization using sulfadiazine, methacrylic acid (MAA), ethylene glycol dimethacrylate (EGDMA), and 2,2'-azobisisobutyronitrile (AIBN) as the template, functional monomer, cross-linker, and initiator respectively. Before polymerization, the ITO electrode was functionalized with 3-aminopropyltriethoxysilane (APTES) to promote covalent attachment of the polymer to the electrode. After polymerization, the template molecule SDZ was removed to create selective recognition sites, forming the molecularly imprinted polymer electrode (MIP/APTES-ITO), which facilitates sulfadiazine detection. The sensor's performance was evaluated using cyclic and differential pulse voltammetry, demonstrating a linear response in the sulfadiazine concentration range 0.1 to 300μM, with a detection limit of 0.11μM. The MIP-based sensor exhibited goodreproducibility, repeatability, selectivity, and stability in sulfadiazine detection. Its practical applicability was confirmed by the successful quantification of sulfadiazine in spiked milk samples.

Synthesis and structural characterization of acrylonitrile/vinyl imidazole copolymers and their amidoximated derivatives

Recently, environmental applications of copolymers such as CO2 capture and separation have become of significant interest. The development of copolymers with basic functional groups, such as amidoxime (AO) groups, represents a successful approach for enhancing absorption and separation of acidic molecules, such as CO2. In this research, acrylonitrile/N-vinyl imidazole (AN/VIM) copolymers were first synthesized through a free radical copolymerization method using 2,2′-azobisisobutyronitrile (AIBN) as the initiator and dimethylformamide as the solvent. The synthesized copolymers were then functionalized using hydroxylamine hydrochloride (NH2OH · HCl), the result being amidoximated (AO) copolymers. The synthesized copolymers were characterized by nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis and Fourier transform infrared spectroscopy. The analytical results simply confirmed that the copolymers and their amidoximated derivatives had successfully been synthesized. A microstructural study of amidoximated polymers using NMR spectroscopy clearly showed the tautomerization of AO groups.

Operando Fabricated Quasi-Solid-State Electrolyte Hinders Polysulfide Shuttles in an Advanced Li-S Battery

Lithium-sulfur (Li-S) batteries are a promising option for energy storage due to their theoretical high energy density and the use of abundant, low-cost sulfur cathodes. Nevertheless, several obstacles remain, including the dissolution of lithium polysulfides (LiPS) into the electrolyte and a restricted operational temperature range. This manuscript presents a promising approach to addressing these challenges. The manuscript describes a straightforward and scalable in situ thermal polymerization method for synthesizing a quasi-solid-state electrolyte (QSE) by gelling pentaerythritol tetraacrylate (PETEA), azobisisobutyronitrile (AIBN), and a dual salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium nitrate (LiNO3)-based liquid electrolyte. The resulting freestanding quasi-solid-state electrolyte (QSE) effectively inhibits the polysulfide shuttle effect across a wider temperature range of −25 °C to 45 °C. The electrolyte’s ability to prevent LiPS migration and cluster formation has been corroborated by scanning electron microscopy (SEM) and Raman spectroscopy analyses. The optimized QSE composition appears to act as a physical barrier, thereby significantly improving battery performance. Notably, the capacity retention has been demonstrated to reach 95% after 100 cycles at a 2C rate. Furthermore, the simple and scalable synthesis process paves the way for the potential commercialization of this technology.

Assessment of Acrylamide Levels by Advanced Molecularly Imprinted Polymer-Imprinted Surface Plasmon Resonance (SPR) Sensor Technology and Sensory Quality in Homemade Fried Potatoes.

This study evaluated acrylamide (AA) levels and various quality parameters in homemade fried potatoes prepared in different sizes by integrating principles from the Slow Food Movement with advanced sensor technology. To this aim, a surface plasmon resonance (SPR) sensor based on a molecularly imprinted polymer (MIP) was first developed for the determination of AA in homemade fried potatoes at low levels, and the AA levels in the samples were established. First of all, monolayer formation of allyl mercaptane on the SPR chip surface was carried out to form double bonds that could polymerize on the chip surface. AA-imprinted SPR chip surfaces modified with allyl mercaptane were prepared via UV polymerization using ethylene glycol dimethacrylate (EGDMA) as a cross-linker, N,N'-azobisisobutyronitrile (AIBN) as an initiator, and methacryloylamidoglutamicacid (MAGA) as a monomer. The prepared AA-imprinted and nonimprinted surfaces were characterized by atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectroscopy methods. The SPR sensor indicated linearity in the range of 1.0 × 10-9-5.0 × 10-8 M with a detection limit (LOD) of 3.0 × 10-10 M in homemade fried potatoes, and the SPR sensor demonstrated high selectivity and repeatability in terms of AA detection. Additionally, the highest AA level was observed in the potato sample belonging to the T1 group, at 15.37 nM (p < 0.05), and a strong and positive correlation was found between AA levels and sensory parameters, the a* value, the ΔE value, and the browning index (BI) (p < 0.05).

Easily water soluble cellulose-based fluorescent probes for the detection of 4-nitrophenol

Cellulose, an abundantly available natural polymer, is generally insoluble in water or common organic solvents. In this study, fluorescent probes based on cellulose were fabricated, rendering them soluble in H2O and capable of selectively recognizing 4-nitrophenol (4-NP). Firstly, the modified cellulose with -Cl was prepared by the substitution reaction of –OH and SOCl2 on cellulose. Secondly, the reversible addition-fragmentation chain transfer (RAFT) reagent FNT with –NO2 and –CHO was obtained by reacting p-nitrophenylthiophenol with p-chloromethyl benzaldehyde. It was then reacted with 2,4-dimethylpyrrole to obtain a fluoroboronodipyrrole fluorescent RAFT reagent BNT with –NO2, followed by the reduction of –NO2 to –NH2 to obtain ABT. RAFT polymerization was conducted using reagent ABT with sodium vinyl sulfonate (SVS), sodium p-styrene sulfonate (SSS), sodium allyl sulfonate (SAS) in DMF. In the polymerization process, azobisisobutyronitrile (AIBN) was used as the initiator, yielded polymers with superior water solubility. Finally, three cellulose based fluorescent probes were prepared by substitutional reaction between -Cl on cellulose and –NH2 on the as-prepared polymers. The solubility of the probes was much higher than that of the original cellulose, and it can be served as macromolecular probes for the detection of 4-NP, and applied in environmental systems.

Determination of Aspirin by Resonance Rayleigh Scattering (RRS) Using a Magnetic Molecularly Imprinted Poly(Methacrylic Acid) Probe

Nanosurface-imprinted polymer nanoprobes (Fe3O4@MIP) were prepared by microwave synthesis using Fe3O4 as a nanosubstrate, aspirin as a template, α-methacrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent, and 2,2'-azobisisobutyronitrile (AIBN) as an initiator. Characterization of Fe3O4@MIP revealed that the spectral probe exhibited strong resonance Rayleigh scattering (RRS) for aspirin. With the increase in aspirin concentration, the RRS energy transfer (RRS-ET) was enhanced, and the signal at 370 nm decreased, providing a linear range from 0.25 to 12.5 μmol/L and a detection limit (DL) of 0.08 μmol/L. The developed protocol was used for the determination of aspirin in drugs with recoveries from 93.2 to 102.6.

A General Approach for the Synthesis of Cyanoisopropyl Bicyclo[1.1.1]pentane (BCP) Motifs by Energy Transfer Process.

Bicyclo[1.1.1]pentane (BCP) heteroaryls make up an important class of BCP derivatives in drug discovery. Herein, we report the visible-light-mediated synthesis of cyanoisopropyl BCP-heteroaryls motifs from N-containing heterocycles, [1.1.1]propellane, and AIBN (2,2'-azobis(isobutyronitrile)) through three-component cascade reaction. Importantly, this protocol is compatible with pyrazinones, quinoxaline-2(1H)-one, azauracils, quinoline derivatives, and imidazo[1,2-b]pyridazine, as well as various phenyl disulfide derivatives; thus, this operationally simple and general methodology could enable rapid library generation of sought-after BCP derivatives for drug development.

Thiram Determination in Milk Samples by Surface Plasmon Resonance Based on Molecularly Imprinted Polymers and Sulphur-Doped Titanium Dioxide.

In this work, a new surface plasmon resonance (SPR) sensor based on sulphur-doped titanium dioxide (S-TiO2) nanostructures and molecularly imprinted polymer (MIP) was presented for thiram (THI) determination in milk samples. Firstly, the S-TiO2 nanomaterial with a high product yield was prepared by using a facile sol-gel hydrolysis technique with a high product yield. After that, UV polymerization was carried out for the preparation of the THI-imprinted SPR chip based on S-TiO2 using a mixture including ethylene glycol dimethacrylate (EGDMA) as the cross-linker, N,N'-azobisisobutyronitrile (AIBN) as the initiator, and methacryloylamidoglutamicacid (MAGA) as the monomer. The reliability of the sensor preparation procedure has been successfully proven by characterization studies of the prepared nanomaterials and SPR chip surfaces through spectroscopic, microscopic, and electrochemical methods. As a result, the prepared SPR sensor showed linearity in the range of 1.0 × 10-9-1.0 × 10-7 M with a detection limit (LOD) of 3.3 × 10-10 M in the real samples, and a sensor technique for THI determination with high sensitivity, repeatability, and selectivity can be included in the literature.

Synthesis, photopolymerization and evaluation of electrical properties of epoxidized castor oil-based acrylates

In this study, synthesis, characterization and photopolymerization of new type of castor oil-based monomer family are studied. Electrical properties of the synthesized polymers are also evaluated. The synthesis of these materials consists of two steps. Acrylation of the castor oil and methyl ricinoleate occur in the first step and epoxidation is then followed. Epoxidized acrylated castor oil (EACO) and epoxidized acrylated methyl ricinoleate (EAMR) are synthesized at the end of the reactions. FTIR (Fourier transform infrared) and 1H NMR (nuclear magnetic resonance) spectroscopy techniques are used to characterize of the starting materials and monomers. When acrylate groups are introduced to castor oil and methyl ricinoleate, a characteristic peak at 1722 cm−1 is observed in FTIR spectrum and peaks of acrylate hydrogens at 5.7, 6.0 and 6.3 are observed in 1H NMR spectrum. After epoxidation, a small peak is detected at 840 cm−1 in FTIR spectrum and new peaks appear at 2.5 and 3.0 ppm in 1H NMR spectrum. Photopolymerization of the synthesized materials are performed with DMPA (2,2-dimethoxy-2-phenylacetophenone) and AIBN (azobisisobutyronitrile) catalyst. It is found that DMPA catalyst is more effective than AIBN. EACO samples’ DC (direct current) resistance and conductance values are measured as 146.4 MΩm and 6.83 nS/m, respectively, whereas EAMR samples’ DC resistance and conductance values are calculated as 96 MΩm and 10.42 nS/m, respectively. AC (alternative current) analysis is conducted by using LCR meter for the polymeric samples where EACO samples’ capacitances varies from 4.88 to 3.29 pF (picofarads) with respect to frequency (10 Hz–300 kHZ). On the other hand, EAMR samples’ capacitances varies from 14.7 to 6.49 pF with respect to frequency. Impedance values of the EACO samples with respect to frequency are measured as 4.24 GΩ and 165 kΩ, respectively. Impedance values of the EAMR samples with respect to frequency are measured as 1.19 GΩ and 82 kΩ, respectively.

Oil absorbent based on lauryl methacrylate grafting onto cellulose of water hyacinth (Eichhornia crassipes)

AbstractIn this article, a novel oil‐absorbent polymer was synthesized by graft polymerization of lauryl methacrylate (LMA) onto water hyacinth (WH) using 2,2′‐azobisisobutyronitrile (AIBN) as initiator and divinyl benzene (DVB) as a crosslinking agent. The effects of initiator content, LMA content, reaction temperature, reaction time, and crosslinker content on the superabsorbent polymer were investigated. The prepared graft copolymer WH‐g‐LMA was analyzed using FTIR, SEM, XRD, and TGA. In the presence of the better cross‐linker DVB (1.5%) and contact time of about 25 min, the maximal Q (oil sorption capacity) of co‐polymer towards crude and Soybean oils is 23.68 and 25.72 g g−1, respectively. The Q is reduced when sorbent dosage increased, but it increases with increasing the temperature and reaches a maximum of 40 °C. The reusability of co‐polymer is characteristic of 7 sorption/desorption cycles.

Polymerization of Thermo-Responsive Poly(N-vinylcaprolactam): Effects of Temperature, Initiator and Monomer Concentration on Percent Conversion

Poly(N-vinyl caprolactam) (PNVCL) is a thermally responsive polymer. Its temperature-responsive properties make it an attractive candidate for various applications. A series of temperature-sensitive PNVCL were synthesized through free radical polymerization, using various of amount of Azobisisobutyronitrile (AIBN) as initiator agent and with reaction temperatures set at 60oC, 70oC, 80oC. The percent conversion of polymerization was determined using the Hubl method to investigate the effects of three factors: initiator agent concentration, monomer concentration and reaction temperature. Furthermore, the chemical structure and the responsiveness of the PNVCL polymer were analyzed using Fourier transform infrared spectroscopy (FTIR) and UV-vis spectrometer, respectively. The study revealed that increasing the reaction temperature, initiator concentration, and monomer concentration resulted in higher percent conversion of polymerization. Finally, the obtained polymer demonstrated thermal sensitivity within the range of 32oC to 38oC, which is close to human body temperature, suitable for biomedical applications.

A Novel Molecularly Imprinted Quartz Crystal Microbalance Sensor Based on Erbium Molybdate Incorporating Sulfur-Doped Graphitic Carbon Nitride for Dimethoate Determination in Apple Juice Samples.

Dimethoate (DIM) as an organophosphorus pesticide is widely utilized especially in the cultivation of vegetables and fruits due to its killing effect on harmful insects. However, unconscious use of DIM in large amounts can also cause serious health problems. For these reasons, rapid and reliable detection of DIM from food samples is significant. In this study, a novel quartz crystal microbalance (QCM) sensor based on erbium molybdate incorporating sulfur-doped graphitic carbon nitride (EM/S-g-C3N4) and a molecularly imprinting polymer (MIP) was designed for DIM detection in apple juice samples. Firstly, an EM/S-g-C3N4 nanocomposite with high purity was prepared under hydrothermal conditions at high temperatures over a long period of time. After the modification of the EM/S-g-C3N4 nanocomposite on a QCM chip, the polymerization solution including N,N'-azobisisobutyronitrile (AIBN) as an initiator, ethylene glycol dimethacrylate (EGDMA) as a cross-linker, methacryloylamidoglutamic acid (MAGA) as a monomer, and DIM as an analyte was prepared. Then, the polymerization solution was dropped on an EM/S-g-C3N4 nanocomposite modified QCM chip and an ultraviolet polymerization process was applied for the formation of the DIM-imprinted polymers on the EM/S-g-C3N4 nanocomposite modified QCM chip. After the polymerization treatment, some characterization studies, including electrochemical, microscopic, and spectroscopic methods, were performed to illuminate the surface properties of the nanocomposite and the prepared QCM sensor. The values of the limit of quantification (LOQ) and the detection limit (LOD) of the prepared QCM sensor were as 1.0 × 10-9 M and 3.3 × 10-10 M, respectively. In addition, high selectivity, stability, reproducibility, and repeatability of the developed sensor was observed, providing highly reliable analysis results. Finally, thanks to the prepared sensor, it may be possible to detect pesticides from different food and environmental samples in the future.

Dual-responsive silicone films loaded with silver particles for potential biomedical applications

Silicone is one of the most widely used polymers in biomedicine because of its versatile use in medical products; it can be modified to improve their properties with potential use in biomedicine. In this research, silicone films were modified by a one-step grafting reaction of N-isopropylacrylamide (NIPAAm) and acrylic acid (AAc) initiated by azobisisobutyronitrile (AIBN) and gamma radiation from a Co-60 source. Variables such as temperature, solvent, reaction time, monomer concentration, dose, and amount of AIBN were studied to determine its influence on the graft. The modified films were characterized by infrared spectroscopy (FTIR-ATR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM-EDS), mechanical tests, and physicochemical studies to determine critical pH and Lower Critical Solution Temperature (LCST). Given the incorporation of the monomers, the synthesis and loading of Ag particles was carried out, through a reaction in water without reducing agents. Finally, the antimicrobial activity of the films synthesized by both methods and loaded with silver was evaluated against S. aureus and E. coli bacteria confirming their in vitro effectiveness.Silicone, acrylic acid, N-isopropylacrylamide, grafting, gamma radiation, silver particles.

PH-tailored monodispersed nanopolystyrene: environmental impact on PGPR and nitrogen cycling in agricultural soils

ABSTRACT Emulsion polymerization was optimized to synthesize polystyrene nanoparticles (NPSt) with tailored sizes by adjusting pH and azobisisobutyronitrile (AIBN) content. An NPSt sample prepared with 20 mg AIBN at pH 8 showed the smallest size (88 nm) and narrowest distribution (24 nm peak width). XRD patterns indicated semi-crystalline nature for this optimized sample. The involvement of synthesized NPSt in the nitrogen (N) cycle enhanced our understanding of nitrogen transformations and the response of microbial populations to polystyrene nanoparticles in the environment. In vitro experiments revealed compatibility of NPSt with tested PGPR strains, with no inhibition zones observed. Furthermore, carrot growth in soil containing 400 mg/kg NPSt showed no significant changes in biomass or shoot height compared to control soil. This demonstrates the NPSt samples had no negative effects on PGPR or soil nitrogen transformations and bacterial communities. Overall, the study optimized the synthesis of NPSt, evaluated environmental impacts on soil nitrogen cycling and PGPR, and found no toxicity of NPSt on PGPR or carrot growth up to 400 mg/kg concentration. The insights contribute to understanding nanomaterial interactions in agricultural systems, highlighting the need to consider the environmental impacts of nanoparticles.

Synthesis of Acrylonitrile-Butadiene-Styrene Copolymers Through Interface-Initiated Room-Temperature Polymerization

Acrylonitrile-butadiene-styrene (ABS) copolymers were synthesized in emulsions and silica-containing emulsion gels at 20, 40, and 60 °C. The room-temperature polymerization was achieved by decomposing 2,2’-azobisisobutyronitrile (AIBN) at oil-water interfaces. The...

Preparation of poly(vinyl alcohol) with enhanced stereoselectivity via hydrolysis of poly(vinyl acetate) produced by radical polymerization using 7-membered ring controlling agents

Controlling tacticity is crucial in polymer chemistry since it impacts the characteristics of synthetic polymers. Poly(vinyl alcohol) (PVA), generally obtained by hydrolysis of poly(vinyl acetate) (PVAc), is a prevalent polymer whose properties are susceptible to even a small change in the main chain stereostructure. Thus, new polymerization methods that improve the tacticity of PVA or its precursor polymer are highly desirable. Herein, 7-membered ring compounds (tropolone (Tro-H), 2-tosyloxytropone (Tro-OTs), potassium tropolonate (Tro-K), methanesulfonic acid, 1,1,1-trifluoro-,7-oxo-1,3,5-cycloheptatrien-1-yl ester (Tro-OTf), potassium 4-((7-oxocyclohepta-1,3,5-trien-1-yl)oxy)butane-1-sulfonate (Tro-SO3K) are explored for the first time as controlling agents for the radical polymerization of VAc with azobisisobutyronitrile (AIBN) as initiator. The obtained PVAc was hydrolyzed to obtain PVA. Process parameters such as monomer concentration, amount of controlling agent and initiators were optimized. The results revealed that the hydrolysis of PVAc produced in the presence of controlling agents gave PVA with improved stereoselectivity. Higher stereoselectivity, that is, isotactic triad (mm) = 24.24% of PVA, was obtained by the hydrolysis of PVAc produced with Tro-SO3K compared to VAc polymerization with other controlling agents. Moreover, hydrolysis of PVAc produced with Tro-SO3K under a wavelength radiation source (λmax, 365 nm) gave PVA with increased mm to 24.59% under similar conditions. In addition, flow chemistry, an emerging technology, was also used for VAc polymerization under optimized reaction conditions to obtain PVA with a mm of 24.62%. This work therefore provides an effective strategy to produce PVA with improved stereoselectivity via both batch and continuous flow techniques, enabling technical advantages for potential large-scale uses.

Characterization of Prasugrel Degradation Profile by Several Oxidative Reagents using HPLC and LC-MS/MS Technique

Prasugrel, a derivative of thienopyridine functions as a prodrug that exerts irreversible inhibition on platelet ADP receptors by specifically targeting the P2Y12 receptor. In pharmaceuticals, the stability of the product plays a crucial role in establishing the shelf life of product. The second common degradation pathway next to hydrolysis is the oxidation. In practice, the oxidative stress studies were carried out using hydrogen peroxide (H2O2), free radicals, oxygen purging, transition metals, singlet oxygen, Fenton reagent, etc. This study compares the oxidative degradation behaviour of prasugrel hydrochloride using different oxidative stressors and was analyzed by HPLC using a method that could separate degradation products individually and from the drug. The degradation products formed under different stress conditions were characterized using LC-TOF-MS/MS. Analysis of accelerated stability samples of prasugrel formulation revealed that the degradation products formed under azobisisobutyronitrile (AIBN) and H2O2 stress conditions were simulated with the stability data. This study on prasugrel showed that the degradation products formed with H2O2 were also observed under hydrolytic conditions. In the pharmaceutical industry, H2O2 is the only oxidative stressor (&lt; 95%) used to study the oxidation degradation of the sample. The present work has demonstrated that AIBN serves as a valuable oxidative stressor for accurately assessing the oxidative stability of drug.

Firefighting Gel Polymer Electrolyte for Non-Flammable Li-Ion Batteries Based on Extremely Low Amount of a Cross-Linkable Polymer

Safety issues of lithium-ion batteries(LIBs) have caught a priority of concerns as the electric vehicle(EV) market expands dramatically and requires higher energy densities. To be free from a variety of unpredictable situations and environments triggering such a safety issue, materials that provide a mechanism to control the factors causing fire and explosion are required to be involved in LIB cells.In this work, we present a gel polymer electrolyte(GPE) characterized by nonflammability and fire-extinguishing capability by radical scavenging(Rs). This GPE was realized within battery cells by in situ crosslinking a small amount of a cross-linkable fluoro-functionalized cyanoethyl polyvinyl alcohol(F7) in conventional carbonate electrolytes having LiPF6. The cyanoethyl functional groups(-CN) is responsible for gelation by cross-linking while the fluorine-containing moiety terminated radical chain reactions triggering thermal runaway by Rs. The strong interaction between the polymer and solvent molecules restricted solvent volatility. The tiny solid content at 2 wt. % in GPE guaranteed a liquid-level ionic conductivity at 9 mS/cm, disallowing battery performances to be sacrificed. Formation of the LiF-dominant solid-electrolyte-interphase(SEI) layer on anodes was encouraged by the fluoro-moiety of F7.In previous research of our group, PVA-CN was used as cross-linkable polymer for enhancement of mechanical property with additional metal-chelating functional group. Hydroxy group of PVA-CN is useful to modify the functional group by DCC coupling mechanism. Herein, as same as previous modification, the Heptafluorobutyric acid(HFB) was used for non-flammability and battery performance. F7 was expected to not only increase thermal stability but also scavenge the radicals. In addition, LiF-rich SEI layers would be made by fluorine groups.First, GPE increase its thermal stability by strong interaction between cross-linked polymer matrix and organic solvents. The binding energy of ethylene carbonate (EC) and hydrogen of cyanoethyl side chain was 0.4 eV which is stronger compared with general hydrogen bond(0.2 eV). Therefore, the flammable gas generation was suppressed by strong interaction between solvents and polymer matrix.In addition, the flash point demonstrated the strong interaction in GPE. The flash point of GPE which contained different polymer contents was decreased as the ratio of polymer content was increased. The composition of the atmosphere in the devices changed into more flammable because of the higher ratio of EMC gas in the atmosphere within enough time to equilibrate. In other words, EC forms a greater number of strong interactions with the polymer matrix while the polymer contents increased. The SET test of 2 wt.% PVA-CN-based GPE(G2)(3.36 s/g) and 5 wt.% PVA-CN-based GPE(G5)(0 s/g) proved that higher contents of PVA-CN in GPE ensure the non-flammability.Second, to overcome the poor electrochemical ability of G5, Rs functionalized F7 was used instead of PVA-CN. Unlike G2, only with 2 wt. % of F7 guaranteed the 0 s/g of SET. Non-flammability of 2 wt.% F7-based GPE(FG2) is due to the fluorine moiety scavenge the O• or H•. In the nail penetration test, only the FG2 was not exploded and maintained charged voltage while the nail penetrates the whole pouch cell vertically because of its elasticity.The Rs capability was demonstrated by cyclic voltammetry(CV) with 2,2’-azobisisobutyronitrile(AIBN) and alpha-tocopherol(α-TOH). After α-TOH react with AIBN radicals at the 70 ℃, the oxidation current decreased because of consumption of α-TOH. The Rs capability was calculated by ratio of current retention of α-TOH oxidation current with a same amount of among scavenger additives. The Rs capability of F7 was 214%.Lastly, our findings suggest sufficient non-flammability without battery performances degradation. The capacity retention of FG2 was higher than LE at the 300th Cycles. This is because the fluorine moiety contributed to make LiF-rich SEI layers. The rigid SEI layers and GPE suppressed volume expansion of graphite. Also, the capacity fade was not observed in FG2 with higher current density. The reason for great rate capability is higher lithium-ion conductivity which is a multiplication of ionic conductivity and lithium-ion transference number(tLi+). FG2has 4.82 of lithium-ion conductivity, while 3.63 in LE. Therefore, the mass transfer resistance was not large on the electrode surface due to the higher lithium-ion mobility in FG2.In this work, the non-flammability and battery performance were successfully demonstrated by thermal stability and Rs capability without any battery performances degradation. The thermal stability was enhanced by strong intermolecular forces between polymer chain and polar organic solvents. The radical chain reaction was terminated by fluorine moiety of GPEs matrix. The capacity retention of FG2 was outstanding compared with LE. Therefore, due to the FG2, the battery will be able to ensure non-flammability without degradation of performance. Figure 1